Certain 2-(2-substituted benzoyl)-1,3,5-cyclohexanetriones

ABSTRACT

Compounds of the formula ##STR1## wherein R 60  is halogen, C 1  -C 4  alkoxy, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, cyano, nitro, S(O) n  R wherein R is C 1  -C 4  alkyl and n is the integer 0, 1 or 2; and R 61  through R 66  are hydrogen or certain substituents, their salts, herbicidal compositions containing the compound or salts and the herbicidal use thereof.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a divisional of application Ser. No. 126,449, filed Nov. 30, 1987 which is now U.S. Pat. No. 4,797,150 which is a continuation-in-part application of Ser. No. 110,988, filed Oct. 21, 1987, now abandoned, which is a divisional application of Ser. No. 880,370, filed June 30, 1987, now U.S. Pat. No. 4,780,127 which is a continuation-in-part application of Ser. No. 872,067, filed June 9, 1986, now abandoned.

Applicants specifically incorporate by reference the contents of the above listed U.S. Patent applications.

BACKGROUND OF THE INVENTION

Compounds having the structural formula ##STR2## wherein X can be alkyl, n can be 0, 1, or 2, and R₁ can be phenyl or substituted phenyl are described in Japanese Patent Application No. 84632-1974 as being intermediates for the preparation of herbicidal compounds of the formula ##STR3## wherein R₁, X, and n are as defined above and R₂ is alkyl, alkenyl, or alkynyl. Specifically taught herbicidal compounds of this latter group are those where n is 2, X is 5,5-dimethyl, R₂ is allyl and R₁ is phenyl, 4-chlorophenyl or 4-methoxyphenyl.

The precursor intermediates for these three specifically taught compounds have no or almost no herbicidal activity.

DESCRIPTION OF THE INVENTION

Embodiment G of this invention relates to 2-benzoyl-1,3,5-cyclohexanetriones and their use as herbicides.

Embodiment G' of this invention is an herbicidal composition comprising an herbicidally active 2-benzoyl-substituted-1,3,5-cyclohexanetrione and an inert carrier therefor. The 4- and 6-positions of the 1,3,5-cyclohexanetrione moiety are preferably substituted with groups hereinafter defined, most preferably with all methyl groups. The benzoyl moiety can be substituted, preferably with the groups hereinafter recited.

The novel compounds of Embodiment G have the following structural formula ##STR4## wherein R⁶⁰ is hydrogen; halogen; C₁ -C₂ alkyl, preferably methyl; C₁ -C₂ alkoxy, preferably methoxy; nitro; cyano; C₁ -C₂ haloalkyl, preferably trifluoromethyl; R^(a) SO_(n) --wherein n is 0 or 2, preferably 2 and R^(a) is C₁ -C₂ alkyl, preferably methyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy. Preferably, R⁶⁰ is chlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, trifluoromethyl, cyano, nitro, C₁ -C₂ alkylthio or C₁ -C₂ alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl; and

R⁶¹ is hydrogen or C₁ -C₄ alkyl, preferably methyl;

R⁶² is hydrogen or C₁ -C₄ alkyl, preferably methyl; or

R⁶¹ and R⁶² together are C₂ -C₅ alkylene;

R⁶³ is C₁ -C₄ alkyl, preferably methyl;

R⁶⁴ is C₁ -C₄ alkyl, preferably methyl; or

R⁶³ and R⁶⁴ together are C₂ -C₅ alkylene;

R⁶⁵ and R⁶⁶ independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n) - wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl;

(11) R^(e) C(O)--wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy;

(12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or

(13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined.

Preferably R⁶⁵ is in the 3-position or 5-position. More preferably R⁶⁵ is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C₁ -C₄ alkoxy, C₁ -C₄ alkyl or C₁ -C₄ thioalkyl. Preferably R⁶⁶ is in the 4-position. Most preferably R⁶⁶ is halogen, cyano, trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl or C₁ -C₄ haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The terms "C₁ -C₄ alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "C₁ -C₄ haloalkyl" includes the alkyl groups defined above under C₁ -C₄ alkyl in which one or more hydrogens is replaced by chlorine, bromine, iodine or fluorine.

Salts of the above-described compounds (as defined hereinafter) are included within the scope of the instant invention.

The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR5## wherein R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵ and R⁶⁶ are as defined above.

The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by reaction with a base to form a salt having an anion of the following four resonance forms: ##STR6## wherein R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵ and R⁶⁶ are as defined above.

Examples of cations of these bases are inorganic cations such as alkalimetals, e.g., lithium, sodium and potassium; the alkaline earth metals, e.g. calcium and magnesium or ammonium or organic cations such as substituted ammonium, sulfonium, sulfoxonium or phosphonium wherein the substituents are aliphatic or aromatic groups.

Those skilled in the art will recognize in considering the salts of this invention that varying degrees os association between the anion and cation will exist depending upon the nature of the cation. In some instances with a suitable cation, such as copper, the salt can exist in a chelated form.

The compounds of this invention and their salts are active herbicides of a general type. That is, they are herbicidally effective against a wide range of plant species. The method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds to the area where control is desired.

The compounds of Embodiment G and G' of the present invention can be prepared by the following two-step general method.

The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR7## wherein R⁶⁰ through R⁶⁶ and moderate base are as defined and X is halogen, preferably chlorine, C₁ -C₄ alkyl--C(O)--O--, C₁ -C₄ alkoxy--C(O)--O-- or ##STR8## wherein R⁶⁰, R⁶⁵ and R⁶⁶ in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C₁ -C₆ alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the trione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably is added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete. ##STR9## wherein the moderate base and R⁶⁰ through R⁶⁶ are as defined above.

Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the moderate base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably about 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 50° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.

The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.

The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases, e.g., trialkylamines such as triethylamine and inorganic bases such as alkali metal carbonates and phosphates. Suitable inorganic bases include potassium carbonate and trisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the crown ethers.

A number of different solvents are useful in this process, depending on the nature of the acid halide or the acylated product. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanide source, the rearrangement may be conducted at temperatures up to about 50° C.

The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR10## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C.A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).

The following are three representative examples of the methods described therein. ##STR11## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR12## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR13## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (c) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.

The following example teaches the synthesis of a representative compound of Embodiment G and G' of this invention.

EXAMPLE 1-G,G' 2-(2'-Nitro-4'-chlorobenzoyl)-4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione ##STR14##

2-Nitro-4-chlorobenzoyl chloride (2.2 g, 10 mmol) and 4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione (1.8 g, 10 mmol) were dissolved in methylene chloride. Triethylamine was added and the resulting solution stirred at room temperature for 30 minutes. The solution was washed with 1 normal hydrochloric acid (1N HCl), and saturated sodium chloride (brine), dried over anhydrous magnesium sulfate (MgSO₄) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (5 ml, 3.5 equivalents) and acetone cyanohydrin (0.5 g, 0.6 equivalent) were added and the mixture stirred at room temperature for 4 hours. After dilution with ether, the solution was washed with 1N HCl and extracted with 5% K₂ CO₃. The basic extract was acidified with HCl and extracted with ether. The ether extract was washed with brine, dried over MgSO₄ and concentrated under vacuum, yielding 2.2 g of crude product.

The following are tables of certain selected compounds of Embodiment G' that are preparable according to the procedures described herein. Compound numbers are assigned to each compound and are used throughout the remainder of the application.

                                      TABLE I-G                                    __________________________________________________________________________      ##STR15##                                                                     Comp.                                                                          No. R.sup.60                                                                            R.sup.61                                                                          R.sup.62                                                                          R.sup.63                                                                          R.sup.64                                                                          R.sup.65                                                                            R.sup.66                                                                               m.p. °C.                              __________________________________________________________________________     1G  NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    H       112-117                                      2G.sup.a                                                                           NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-Cl    76-82                                        3G  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 CH.sub.3                                                                    176-179                                      4G  CH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 C.sub.2 H.sub.5                                                             gum                                          5G  CH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CF.sub.3                                                                             viscous oil                                  6G  NO.sub.2                                                                            CH.sub. 3                                                                         CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 CH.sub.2 Cl                                                                 oil                                          7G  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-F     gum                                          8G  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5                                                             gum                                          9G  NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 CH.sub.3                                                                    gum                                          10G Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SCH.sub.3                                                                            gum                                          11G CH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-NO.sub.2                                                                          H       gum                                          12G I    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    H       gum                                          13G OCH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-Cl    gum                                          14G Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OCH.sub.3                                                                         4-Br    gum                                          15G NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 nC.sub.3 H.sub.7                                                            gum                                          16G NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 N(CH.sub.3).sub.2                                                           gum                                          17G NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CN    148-150                                      18G SO.sub.2 CH.sub.3                                                                   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    H       gum                                          19G NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CF.sub.3                                                                             gum                                          20G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-Cl    gum                                          21G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SCF.sub.3                                                                            gum                                          22G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-OCF.sub.3                                                                            gum                                          23G Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-Cl 4-SO.sub.2 C.sub.2 H.sub.5                                                             gum                                          24G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-C(O)CH.sub.3                                                                         gum                                          25G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2CH.sub.3                                                                     129-131                                      26G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SCH.sub.3                                                                            89-92                                        27G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CF.sub.3                                                                             115-125                                      28G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CN    87-95                                        __________________________________________________________________________      .sup.a prepared in Example 1G,G'.                                        

                                      TABLE I                                      __________________________________________________________________________      ##STR16##                                                                     Comp.                                                                          No. R    R.sup.1                                                                           R.sup.2                                                                           R.sup.3                                                                           R.sup.4                                                                           R.sup.5   R.sup.6                                                                              m.p. °C.                           __________________________________________________________________________     29  NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-F   115-118                                   30  NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-SCH.sub.3                                                                          119-123                                   31  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-SC.sub.2 H.sub.5                                                                   oil                                       32  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-SC.sub.3 H.sub.7                                                                   oil                                       33  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-N(C.sub.2 H.sub.5)COCH.sub.3                                                           4-NO.sub.2                                                                           oil                                       34  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-SC.sub.2 H.sub.5                                                                       4-SO.sub.2 C.sub.2 H.sub.5                                                           oil                                       35  NO.sub.2                                                                            H  H  CH.sub.3                                                                          CH.sub.3                                                                          H         H     145-149                                   36  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-Cl  gum                                       37  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         H     glass                                     38  Br   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         H     glass                                     39  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          4-Cl      5-Cl  glass                                     40  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-Cl      5-Cl  glass                                     41  CH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-CH.sub.3                                                                           76-79                                     42  CH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         H     60-61                                     43  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         5-Br  100-105                                   44  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-NO.sub.2                                                                           72-75                                     45  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         5-NO.sub.2                                                                           103-105                                   46  NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         5-CH.sub.3                                                                           136-139                                   47  Br   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OC.sub.2 H.sub.5                                                                       4-SC.sub.3 H.sub.7                                                                   oil                                       48  SCH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OC.sub.2 H.sub.5                                                                       4-SCH.sub.3                                                                          oil                                       49  Br   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OC.sub.2 H.sub.4 OCH.sub.3                                                             4-Br  oil                                       50  Br   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OC.sub.2 H.sub.5                                                                       4-SO.sub.2 C.sub.3 H.sub.7                                                           oil                                       51  SOCH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OCH.sub.3                                                                              4-SOCH.sub.3                                                                         135-142                                   52  NO.sub.2                                                                            C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         H     108-112                                   53  NO.sub.2                                                                            C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-CF.sub.3                                                                           glass                                     54  Cl   C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-SO.sub.2 CH.sub.3                                                                  glass                                     55  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         5-Cl  96-98                                     56  NO.sub.2                                                                            C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-Cl  glass                                     57  Cl   C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-Cl  glass                                     58  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-Cl      4-Cl  105-110                                   59  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-Br  glass                                     60  NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         5-Cl  125-128                                   61  Br   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OC.sub.3 H.sub.7                                                                       4-SC.sub.2 H.sub.5                                                                   oil                                       62.sup.b                                                                           NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         H     80-85                                     63.sup.c                                                                           NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         H     oil                                       64.sup.d                                                                           NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H         4-F   oil                                       __________________________________________________________________________      .sup.b As the sodium salt.                                                     .sup.c As the triethylammonium salt.                                           .sup.d As the potassium salt.                                            

HERBICIDAL SCREENING TESTS

As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. Selected compounds of this invention were tested as herbicides in the following manner.

Pre-emergence herbicide test.

On the day preceding treatment, seeds of seven different weed species are planted in loamy sand soil in individual rows using one species per row across the width of a flat. The seeds used are green foxtail (FT) (Setaria viridis), watergrass (WG) (Echinochloa crusgalli), wild oat (WO) (Avena fatua), annual morningglory (AMG) (Ipomoea lacunosa), velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassica juncea) and yellow nutsedge (YNG) (Cyperus esculentus). Ample seeds are planted to give about 20 to 40 seedlings per row, after emergence, depending upon the size of the plants.

Using an analytical balance, 600 milligrams (mg) of the compound to be tested are weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 60 milliliter (ml) wide-mouth clear bottle and dissolved in 45 ml of acetone or substituted solvent. Eighteen ml of this solution are transferred to a 60 ml wide-mouth clear bottle and diluted with 22 ml of a water and acetone mixture (19:1) containing enough polyoxyethylene sorbitan monolaurate emulsifier to give a final solution of 0.5% (v/v). The solution is then sprayed on a seeded flat on a linear spray table calibrated to deliver 80 gallons per acre (748 L/ha). The application rate is 4 lb/acre (4.48 Kg/ha).

After treatment, the flats are placed in the greenhouse at a temperature of 70° to 80° F. and watered by sprinkling. Two weeks after treatment, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete control.

The results of the tests are shown in the following Tables

                  TABLE II-G                                                       ______________________________________                                         Pre-Emergence Herbicidal Activity                                              Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.   FT      WG     WO    AMG   VL    MD    YNS                               ______________________________________                                          1G   100     100    90    100   100   100   80                                 2G   100     100    90    100   100   100   80                                 3G   100     100    90    100   100   100   80                                 4G   100     100    90    100   100   100   80                                 5G   100     100    90    100   100   100   80                                 6G*  100     100    100   100   100   --    20                                 7G   100     100    80    100   100   100   80                                 8G    85     100    80    100   100   100   80                                 9G   100     100    80    100   100   100   80                                10G   100     100    80    100   100   100   80                                11G   100     100    80    100   100   100   80                                12G   100     100    80     90   100   100    0                                13G   100     100    70    100   100   100    0                                14G   100     100    75    100   100   100   90                                15G   100     100    80    100   100   100   90                                16G   100     100    90    100   100   100   80                                17G   100     100    80    100   100   100   80                                18G   100     100    90     85   100   100   80                                19G   100     100    100   100   100   100   80                                20G    70      95    10    100   100   100    0                                21G   100     100    100   100   100   100   80                                22G   100     100    90    100   100   100   80                                23G   100     100    100   100   100   100   80                                24G    0       80     0     25    80    70    0                                25G   100     100    80    100   100   100   80                                26G   100     100    100    80   100   100   80                                27G   100     100    100   100   100   100   80                                28G   100     100    90    100   100   100   80                                29    100     100    100   100   100   100   80                                30    100     100    100   100   100   100   100                               31    100     100    100   100   100   100   80                                32    100     100    100   100   100   100   80                                33    100     100    85     40   100   100   60                                34    100     100    100    95   100   100   80                                47    100     100    100   100   100   100   80                                48    100     100    100   100   100   100   80                                49    100     100    100   100   100   100   80                                50    100     100    100   100   100   100   80                                51    100     100    100   100   100   100   80                                52    100     100    100   100   100   100   80                                53    100     100    100   100   100   100   100                               58    100     100    100   100   100   100   80                                60    100     100    100   100   100   100   80                                62    100     100    100   100   100   100   80                                63    100     100    100   100   100   100   80                                64    100     100    100   100   100   100   80                                ______________________________________                                          A blank (--) indicates that the weed was not tested.                           *Tested at 0.56 kg/ha.                                                   

Post-Emergence Herbicide Test

This test is conducted in an identical manner to the testing procedure for the pre-emergence herbicide test, except the seeds of the seven different weed species are planted 10-12 days before treatment. Also, watering of the treated flats is confined to the soil surface and not to the foliage of the sprouted plants.

The results of the post-emergence herbicide test are reported in Table III.

                  TABLE III-G                                                      ______________________________________                                         Post-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.   FT      WG     WO    AMG   VL    MD   YNG                                ______________________________________                                          1G   100     95     90    90    100   100  80                                  2G   100     100    100   100   100   100  80                                  3G   100     100    95    100   100   100  90                                  4G   100     100    100   100   100   100  90                                  5G   100     100    100   100   100   100  100                                 6G*  10      80     50    75    40    --    0                                  7G   70      75     70    90    90    80   80                                  8G   50      80     70    90    90    80   30                                  9G   70      80     70    90    90    80   30                                 10G   75      80     70    80    60    50   70                                 11G   70      80     70    80    80    80   80                                 12G   100     75     90    75    80    80   80                                 13G   60      70     70    100   100   100  80                                 14G   20      70     40    60    80    80   70                                 15G   90      70     70    75    80    90   70                                 16G   50      70     80    60    80    90   70                                 17G   90      60     70    65    80    80   80                                 18G   30      50     80    95    95    80   70                                 19G   100     100    95    90    100   100  80                                 20G   10      40      5    70    80    90   70                                 21G   95      90     95    95    100   100  70                                 22G   80      90     90    80    100   100  70                                 23G   90      80     80    80    90    80   30                                 24G    0      30      0    40    80    20    0                                 25G    0      20      0    10    10    20    0                                 26G   80      70     70    80    80    80   70                                 27G   90      90     90    80    80    90   60                                 28G   70      65     50    80    80    80   70                                 29    90      80     60    80    80    80   80                                 30    90      80     80    80    80    80   80                                 31    100     80     80    80    90    80   80                                 32    90      80     80    80    80    80   30                                 33    30      50     60    40    60    30    0                                 34    100     100    85    100   100   100  30                                 47    100     100    100   100   100   100  60                                 48    100     100    100   100   100   100  70                                 49    100     100    100   100   100   100  60                                 50    100     100    100   100   100   100  50                                 51    100     100    100   100   100   100  30                                 52    100     100    100   100   100   100  80                                 53    100     100    100   100   100   100  80                                 58    100     100    100   100   100   100  90                                 60    100     90     90    90    100   100  80                                 62    100     80     60    80    90    80   80                                 63    90      80     60    80    90    80   80                                 64    100     80     60    90    90    90   80                                 ______________________________________                                          A blank (--) indicates the weed was not tested.                                *Tested at 0.56 kg/ha.                                                   

Pre-Emergence Multi-Weed Herbicide Test

Several compounds were evaluated at an application rate of 0.25 lb/acre (0.275 kg/ha) for pre-emergence activity against a larger number of weed species.

The process was generally similar to the pre-emergence herbicide test described above except that only 37.5 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.

Indian mustard (MD) was eliminated in this test and the following weed species were added:

    ______________________________________                                         Grasses:                                                                              annual ryegrass                                                                              Lolium multiflorum                                                                            (ARG)                                             rox-orange sorghum                                                                           Sorghum bicolor                                                                               (SHC)                                             broadleaf     Brachiaria platyphylla                                                                        (BSG)                                             signalgrass                                                                    hemp sesbania Sesbania exaltata                                                                             (SESB)                                            nightshade    Solanum sp.    (SP)                                              cocklebur     Xattiium sp.   (CB)                                       ______________________________________                                    

The results of this 0.275 kg/ha test are shown in Table IV-G.

Post-Emergence Multi-Weed Herbicide Test

Several compounds were evalated at an application rate of 0.25 lb/acre (0.275 kg/ha) for post-emergence activity against the larger number of weed species that are used in the pre-emergent multi-herbicide test.

The process was generally similar to the post-emergence herbicide test described above except that only 37.5 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.

The results of this 0.275 kg/ha test are shown in Table V-G.

                                      TABLE IV-G                                   __________________________________________________________________________     Pre-Emergence Multi-Weed Herbicidal Activity                                   Application Rate - 0.275 kg/ha                                                 Cmpd.                                                                          No. FT ARG WG SHC                                                                               WO BSG AMG SESB                                                                               VL SP YNS                                                                               CB                                    __________________________________________________________________________     35  0  0   0  0  0  0   0   0   20 0  0  0                                     36  100                                                                               0   100                                                                               40 40 70  100 90  100                                                                               0  90 35                                    37  100                                                                               80  100                                                                               100                                                                               100                                                                               90  100 100 100                                                                               50 100                                                                               100                                   38  100                                                                               60  100                                                                               90 100                                                                               75  85  100 100                                                                               25 95 100                                   39  95 100 100                                                                               90 100                                                                               50  100 100 100                                                                               20 10 100                                   40  100                                                                               70  100                                                                               60 50 15  90  100 100                                                                               10 40 20                                    41  95 0   70 25 0  0   95  70  75 25 75 70                                    42  65 15  95 25 10 40  40  50  100                                                                               0  90 30                                    43  100                                                                               20  85 100                                                                               100                                                                               70  100 100 100                                                                               0  90 100                                   44  0  0   100                                                                               30 50 20  75  100 100                                                                               0  20 10                                    45  50 0   0  10 0  0   80  0   100                                                                               0  15 40                                    46  100                                                                               10  100                                                                               75 0  30  100 100 100                                                                               0  100                                                                               100                                   54  5  40  100                                                                               40 30 90  98  90  100                                                                               0  50 10                                    55  25 5   100                                                                               95 80 85  100 60  100                                                                               0  80 20                                    56  98 20  95 90 60 50  90  20  100                                                                               0  70 30                                    57  0  0   90 75 5  10  80  20  100                                                                               0  10 20                                    __________________________________________________________________________      (--) = Not Tested.                                                       

                                      TABLE VI-A                                   __________________________________________________________________________     Post-Emergence Multi-Weed Herbicidal Activity                                  Application Rate - 0.25 kg/ha                                                  Cmpd.                                                                          No. FT ARG WG SHC                                                                               WO BSG AMG SESB                                                                               VL SP YNS                                                                               CB                                    __________________________________________________________________________     35  0  0   15 0  10 0   0   20  35 0  0  0                                     36  100                                                                               0   85 35 35 85  100 100 100                                                                               25 35 100                                   37  90 15  90 25 90 85  100 85  100                                                                               60 40 100                                   38  100                                                                               20  70 30 60 70  95  90  95 10 70 100                                   39  40 80  90 25 95 90  100 90  80 35 35 --                                    40  60 70  90 15 75 70  75  85  50 10 50 75                                    41  80 0   90 0  0  35  80  75  75 50 30 85                                    42  30 0   75 25 10 25  75  90  90 10 40 75                                    43  90 0   98 35 95 95  100 100 95 20 20 100                                   44  10 0   25 10 15 0   10  30  20 10 0  0                                     45  40 0   60 25 0  0   40  30  15 0  0  10                                    46  100                                                                               0   95 10 0  0   85  95  100                                                                               0  95 --                                    54  80 15  75 25 75 85  90  95  90 20 30 90                                    55  95 5   80 25 90 85  95  100 100                                                                               0  50 100                                   56  100                                                                               10  95 50 90 75  100 95  100                                                                               50 30 --                                    57  80 0   50 10 0  10  80  100 100                                                                               10 15 60                                    __________________________________________________________________________      (--) = Not Tested.                                                       

The compounds of the present invention and their salts are useful as herbicides and can be applied in a variety of ways at various concentrations. In practice, the compounds or salts are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds or salts can be formulated as granules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as flowables, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient. A herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from about 0.01 to approximately 10 pounds per acre, preferably from about 0.02 to about 4 pounds per acre.

Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. The wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. Wettable powders normally are prepared to contain about 5% to about 95% of the active ingredient and usually also contain a small amount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound or salt with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthal, isophorone and other non-volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises about 0.5% to 95% of active ingredient by weight of the herbicidal composition.

Granular formulations wherein the toxicant is carried on relatively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant. Granular formulations normally are prepared to contain about 0.1% to about 25% of active ingredients which may include surface-active agents such heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.

Typical wetting, dispersing or emulsifying agents and adjuvants used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols, esters and fatty amines; and other types of surface-active agents, many of which are available in commerce. The surface-active agent, when used, normally comprises from 0.1% to 30% by weight of the herbicidal composition.

Dusts, which are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating application.

Pastes, which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5% to about 95% of active ingredient by weight, and may also contain small amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the area to be affected.

Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as water, acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.

The phytotoxic compositions of this invention can be applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray or by rope wick applications because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions can be applied to the soil according to conventional methods and can be distributed in the soil to a depth of at least 1/2 inch below the soil surface. It is not necessary that the phytotoxic compositions be mechanically admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations. In the following examples the herbicidal compound can be substituted with the herbicidal salt of the compound.

    __________________________________________________________________________     General Formula with Ranges                                                                         Specific Formula                                          __________________________________________________________________________     EMULSIFIABLE CONCENTRATE FORMULATIONS                                          Herbicidal compound                                                                            5-55 herbicidal compound                                                                          24                                          surfactant(s)   5-25 proprietary blend of oil-                                                                    10                                          solvent(s)     20-90 soluble sulfonates and                                                   100%  polyoxyethylene ethers                                                         polar solvent                                                                                27                                                               petroleum hydrocarbon                                                                        39                                                                            100%                                         WETTABLE POWDER FORMULATIONS                                                   herbicidal compound                                                                            3-90 herbicidal compound                                                                          80                                          wetting agent  0.5-2 sodium dialkyl naphthalene                                                                   0.5                                         dispersing agent                                                                              1-8   sulfonate                                                 diluent(s)     8.5-87                                                                               sodium lignosulfonate                                                                        7                                                          100%  attapulgite clay                                                                             12.5                                                                          100%                                         EXTRUDED GRANULAR FORMULATIONS                                                 herbicidal compound                                                                            1-20 herbicidal compound                                                                          10                                          binding agent   0-10 lignin sulfonate                                                                             5                                           diluent(s)     70-99 calcium carbonate                                                                            85                                                         100%               100%                                         FLOWABLE FORMULATIONS                                                          herbicidal compound                                                                           20-70 herbicidal compound                                                                          45                                          surfactant(s)   1-10 polyoxyethylene ether                                                                        5                                           suspending agent(s)                                                                           0.05-1                                                                               attagel       0.05                                        antifreeze agent                                                                               1-10 propylene glycol                                                                             10                                          antimicrobial agent                                                                            1-10 1,2-benzisothiazoline-3-one                                                                  0.03                                        antifoam agent 0.1-1 silicone defoamer                                                                            0.02                                        solvent         7.95-77.85                                                                          water         39.9                                                       100%               100%                                         __________________________________________________________________________

When salts are used as the active ingredient in the herbicidal compositions of this invention it is recommended to use salts that are agriculturally acceptable.

The phytotoxic compositions of this invention can also contain other additives, for example, fertilizers, other herbicides and other pesticides, used as adjuvant or in combination with any of the above-described adjuvants. Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. 

What is claimed is:
 1. The method of controlling undesirable vegetation comprising applying to the area where control is desired, an herbicidally effective amount of a compound having the formula ##STR17## wherein R⁶⁰ is hydrogen; halogen; C₁ -C₂ alkyl; C₁ -C₂ alkoxy; nitro; cyano; C₁ -C₂ haloalkyl; or R^(a) SO_(n) - wherein n is 0 or 2 and R^(a) is C₁ -C₂ alkyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy;R⁶¹ is hydrogen or C₁ -C₄ alkyl; R⁶² is hydrogen or C₁ -C₄ alkyl; or R⁶¹ and R⁶² together are C₂ -C₅ alkylene; R⁶³ is C₁ -C₄ alkyl; R⁶⁴ is C₁ -C₄ alkyl; or R⁶³ and R⁶⁴ together are C₂ -C₅ alkylene; R⁶⁵ and R⁶⁶ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) - wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; and (13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined and their salts.
 2. The method of claim 1 wherein R⁶⁰ is hydrogen, chlorine, bromine, methyl, methoxy, nitro, trifluoromethyl, or methylsulfonyl; R⁶¹, R⁶², R⁶³ and R⁶⁴ are methyl; R⁶⁵ and R⁶⁶ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) - wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C.sub. 4 alkoxy; or (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or (13) --N--(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined.
 3. The method of claim 2 wherein R⁶⁵ and R⁶⁶ are independently are hydrogen; chlorine; fluorine; bromine; methyl; C₁ -C₄ alkoxy; trifluoromethoxy; cyano; nitro; trifluoromethyl; R^(b) SO_(n) - wherein n is the integer 0 or 2 and R^(b) is methyl, chloromethyl, trifluoromethyl, ethyl, or n-propyl; R^(e) C(O)- where R^(e) is C₁ -C₄ alkyl; or SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined and R⁶⁵ is in the 3-position or 5-position and R⁶⁶ is in the 4-position.
 4. The method of claim 2 wherein R⁶⁵ is hydrogen and R⁶⁶ is hydrogen, chlorine, bromine, fluorine, cyano, trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl.
 5. The method of claim 2 wherein R⁶⁰ is nitro, R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen; and R⁶⁶ is hydrogen.
 6. The method of claim 2 wherein R⁶⁰ is nitro; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen; and R⁶⁶ is 4-chlorine.
 7. The method of claim 2 wherein R⁶⁰ is chlorine; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-SO₂ CH₃.
 8. The method of claim 2 wherein R⁶⁰ is methyl; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-SO₂ C₂ H₅.
 9. The method of claim 2 wherein R⁶⁰ is trifluoromethyl; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-trifluoromethyl.
 10. The method of claim 2 wherein R⁶⁰ is nitro, R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-SO₂ CH₃.
 11. The method of claim 2 wherein R⁶⁰ is hydrogen; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen; and R⁶⁶ is 4-trifluoromethylthio.
 12. The method of claim 2 wherein R⁶⁰ is nitro; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-cyano.
 13. The method of claim 2 wherein R⁶⁰ is nitro; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen and R⁶⁶ is 4-SO₂ -n-C₃ H₇.
 14. The method of claim 2 wherein R⁶⁰ is nitro; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is hydrogen; and R⁶⁶ is 4-trifluoromethyl.
 15. The method of claim 2 wherein R⁶⁰ is chlorine; R⁶¹ is methyl; R⁶² is methyl; R⁶³ is methyl; R⁶⁴ is methyl; R⁶⁵ is 3-ethoxy; and R⁶⁶ is 4-SO₂ CH₂ CH₃.
 16. The method of claim 2 wherein R⁶⁵ is hydrogen.
 17. The method of claim 2 wherein R⁶⁵ is hydrogen. 